JP2005513170A - Electroactive fluorene polymers having perfluoroalkyl groups, methods for preparing such polymers and devices made with such polymers - Google Patents

Abstract

  The present invention relates generally to perfluoroalkylated fluorene polymers. It further relates to a method for preparing the polymer and devices made with the polymer.

Description

  The present invention relates to electroactive fluorene polymers having perfluoroalkyl groups and to methods for producing such polymers. The invention further relates to an electronic device comprising such a polymeric material therein.

  Organic electronic devices exist in many different types of electronic equipment. In all such devices, an organic active layer is sandwiched between two electrical contact layers. Examples of organic electronic devices include devices that emit light, such as light emitting diodes (LEDs) that make up a display. In an LED, at least one of the electrical contact layers is light transmissive so that light can pass through the electrical contact layer. The organic active layer emits light through the light transmissive electrical contact layer when electricity is applied in the electrical contact layer.

  It is well known to use organic electroluminescent compounds as the active component of light emitting diodes. Simple organic molecules such as anthracene, thiadiazole derivatives, and coumarin derivatives are known to exhibit electroluminescence. Several classes of luminescent polymers have also been disclosed. These include, for example, poly (1,4-phenylene vinylene) and derivatives, polythiophenes, in particular poly (3-alkylthiophene), and poly (p-phenylene). Alkyl and dialkyl derivatives of polyfluorenes have also been disclosed, as in US Patent Publication (Patent Document 1) and US Patent Publication (Patent Document 2).

US Pat. No. 5,708,130 US Pat. No. 5,900,327 US Pat. No. 5,962,631 PCT Application Publication WO 00/53565 Pamphlet US Pat. No. 4,356,429 US Pat. No. 4,539,507 US Pat. No. 5,247,190 US Pat. No. 5,408,109 US Pat. No. 5,317,169 Yamamoto, Progress in Polymer Science 17 (1992), p. 1153. By Colon et al., Journal of Polymer Science, Part A, Polymer Chemistry Edition (Polymer Science Journal, Part A, Polymer Chemistry) 28 (1990), page 367. N. Kamigata, T .; Fukushima, M .; Yoshida, J. Chem. Soc. Perkin Trans. 1 (1989), 1559 pages. “Flexible light-emitting diodes made from soluble conducting polymer”, Nature 357 (June 11, 1992), pages 477-479. Markus, John, “Electronics and Nucleonics Dictionary”, McGraw-Hill, 1966, pages 470 and 476. G. Yu. K. Pakbaz, A.M. J. et al. Heeger, “Optocoupler made semiconductor polymers (optocouplers made from semiconducting polymers)”, Journal of Electronic Materials (Electronic Materials Journal) 22 (1994), pages 925-928. J. et al. J. et al. M.M. Hall et al. (Cambridge Group), “Efficient Photodiodes from Interpolating Polymer Networks”, Nature 376 (1995), pages 498-500.

  There is a continuing need for photoactive compounds with improved efficiency and methods for preparing them.

  The present invention relates to polymers of fluorene and fluorene derivatives having a perfluoroalkyl substituent on the aromatic ring.

In one embodiment, the fluorene polymer is a polymer comprising one or more monomer units having the formula I shown in FIG.
Where
R is a substituent on a carbon atom in the aromatic ring, which may be the same or different at each occurrence, and is hydrogen, alkyl, aryl, heteroalkyl, heteroaryl, F, —CN, —OR ¹ , _{^{-CO 2 R 1, -C Ψ H}} θ F λ, -OC Ψ H θ F λ, -SR 1, -N (R 1) 2, -P (R 1) 2, -SOR 1, -SO 2 R ¹ , —NO ₂ , and R-groups selected or selected from beta-dicarbonyl having the formula XII as shown in FIG. 12 and further described below under “Formula XII” A 5- or 6-membered ring selected from cycloalkyl, aryl, and heteroaryl rings,
Wherein R ¹ is a substituent on the heteroatom that may be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl, and ψ is between 1 and 20 And θ and λ are the following equations A1:
θ + λ = 2Ψ + 1 (Equation A1)
Is an integer that satisfies
R ² is a substituent on a carbon atom not in the aromatic ring that may be the same or different at each occurrence, and is hydrogen, alkyl, aryl, heteroalkyl, heteroaryl, and —C _ψ H _θ F _λ Selected from

However, the fluorene polymer, _(where, [psi than is intended as defined above) wherein _{-C Ψ} F 2Ψ _{+ 1} contains at least one R substituent having.

In another embodiment, the fluorene polymer comprises at least one first monomer unit having the formula I shown in FIG. 1 and at least one second monomer unit, wherein the second monomer unit is ( i) an aromatic group having the formula II shown in FIG. 2, (ii) a 6-membered heteroaromatic group having the formula III shown in FIG. 6, and (iii) a 5-membered ring having the formula IV shown in FIG. A heteroaromatic group, (iv) an aromatic group having the formula V shown in FIG. 8, (v) a divalent having the formula VI to formula VIII shown in FIG. 9, and a formula IX to formula XI shown in FIG. Selected from fused ring aromatic groups, and (vi) combinations thereof;
here,
In each of formulas II, III, IV, V, VI, VII, VIII and IX:
R, R ¹ , R ² , Ψ, θ and λ are as defined above in formula I;
E can be the same or different at each occurrence and is a single bond or a linking group selected from arylene and heteroarylene;
In formula IV:
A is independently C or N at each occurrence, and γ is an integer selected from 0 or 1 or 2, where when both A are N, γ is 0, or A Γ is 1 when one of N is N and one of A is C, or γ is 2 when both A are C;
Q is O, S, SO ₂ or NR ¹ (where
R ¹ is a substituent on the heteroatom that may be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl)
In formula V:
Q ¹ is a carbonyl group, O, S, SO ₂ , or NR ¹ (wherein
R ¹ is a substituent on the heteroatom that may be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl)
W is H, alkyl or heteroalkyl, or both W together can represent a single bond;
In Formula VI:
The two E's are in the 1,4-, 1,5-, 1,8-, 2,3-, or 2,6-position;
In Formula VII:
The two E's are in the 1,4-, 1,5-, 1,8-, 2,3-, 2,6-, or 9,10-position;
In Formula VIII:
The first E is in the 1, 2, or 3rd position, the second E is in the 6, 7 or 8th position,
In formula IX:
The first E is in the 2, 3, or 4th position, the second E is in the 7, 8, or 9th position, and
In Formula XII:
R ³ is selected from hydrogen, alkyl, aryl, heteroalkyl and heteroaryl;
δ is 0 or an integer from 1 to 12,
However, the fluorene polymer, comprising at least one R substituent of the formula _{-C Ψ} F 2Ψ _{+ 1 (where,} [psi are as defined above).

The present invention further provides a method for preparing a fluorene polymer having a perfluoroalkyl group comprising:
Forming a polymer having at least one monomer unit having the formula I shown in FIG.
Treating the polymer with a perfluoroalkylating agent selected from (i) perfluoroalkyl iodide and (ii) perfluoroalkylsulfonyl chloride in the presence of a ruthenium (II) catalyst.

  The invention further relates to an organic electronic device having at least one light emitting layer comprising the above perfluoroalkylated fluorene polymer.

  As used herein, the term “alkyl” is intended to mean a group derived from an aliphatic hydrocarbon, straight chain, branched and optionally substituted or unsubstituted. Contains a cyclic group. The term “heteroalkyl” means a group derived from an aliphatic hydrocarbon having at least one heteroatom in the main chain, which may be unsubstituted or substituted. Intended. The term “aryl” is intended to mean a group derived from an aromatic hydrocarbon which may be unsubstituted or substituted. The term “heteroaryl” is intended to mean a group derived from an aromatic group containing at least one heteroatom, which may be unsubstituted or substituted. The term “arylene” is intended to mean a group derived from an aromatic hydrocarbon having two points of attachment, which may be unsubstituted or substituted. The term “heteroarylene” means a group derived from an aromatic group having at least one heteroatom and having two points of attachment, which may be unsubstituted or substituted. Intended to be. The phrase “adjacent to” when used to refer to a layer in a device does not necessarily mean that one layer is immediately adjacent to another layer. On the other hand, the phrase “adjacent R groups” is used to refer to R groups that are next to each other in a chemical formula (ie, R groups that are on atoms joined by a bond). The terms “fluorene polymer” and “perfluoroalkylated fluorene polymer” are intended to mean both homopolymers and copolymers. The term “base fluorene polymer” is intended to mean a fluorene polymer without any perfluoroalkyl groups. The term “photoactive” refers to any material that exhibits electroluminescence and / or photosensitivity. The term “electroactive” refers to any material that exhibits hole transport / injection properties, electron transport / injection properties, electroluminescence, and / or photosensitivity. The term “monomer unit” refers to a repeating unit in a polymer. In addition, the IUPAC numbering system is used throughout, with the periodic table families numbered 1 to 18 from left to right (CRC Handbook of Chemistry and Physics, CRC and Handbook of Chemistry and Physics), 81st edition, 2000 ).

  The fluorene polymers of the present invention comprise other fragrances comprising at least one fluorene-based monomer unit (Formula I) and at least one of the aromatic rings in the polymer being substituted with at least one perfluoroalkyl group. Group monomer units (formulas II, III, IV, V, VI, VII, VIII, IX, X, and XI) may be included.

(First monomer unit)
The base fluorene polymer has at least a first monomer unit having the formula I shown in FIG. The fluorene polymer can be a copolymer of two or more different monomer units having the formula I. Preferred R groups are alkyl groups having 1 to 30 carbon atoms, heteroalkyl groups having 1 to 30 carbon atoms and one or more S, N, or O heteroatoms, 6 to 20 An aryl group having 1 carbon atom (or alternatively 6 to 18 carbon atoms), and 2 to 20 carbon atoms (or alternatively 2 to 18 carbon atoms) and one or more S, A heteroaryl group having N or O heteroatoms. Examples of suitable R groups include n- and iso-butyl, pentyl, linear and branched, octyl, including hexyl, 2-ethylhexyl, with and without olefinic unsaturation, up to hexadecyl. And above, phenyl, thiophene, carbazole, alkoxy, phenoxy and cyano groups. More preferred R groups on the phenyl ring of the fluorene monomer unit are H, C ₁ -C ₁₂ alkoxy (or alternatively C ₁ -C ₄ alkoxy or C ₆ -C ₁₂ alkoxy), phenoxy, C ₁ -C ₁₂ alkyl ( _{Alternatively,} C 1 -C ₄ alkyl or _C 6 _{-C 12} alkyl), phenyl or cyano.

Preferred R ² groups are alkyl groups having 1 to 30 carbon atoms and heteroalkyl groups having 1 to 30 carbon atoms and one or more S, N, or O heteroatoms. . More preferred R ² groups are linear C ₆ -C ₁₂ alkyl (alternatively straight chain C ₆ -C ₁₀ alkyl) and branched C ₆ -C ₁₂ alkyl (alternatively branched C _6- is selected from C ₁₀ alkyl).

  An example of a suitable first monomer unit is shown as Formula I (a) in FIG.

(Second monomer unit)
Formula II, III, IV, V, VI, VII, VIII, and IX, wherein any one or more of the E linking groups is selected from heteroarylene, wherein the arylene is then represented by Formula XIII shown in FIG. And a group having XIV, where
In Formula XIII:
R is as described above for each of I, II, III, IV, V, VI, VII, VIII to XI;
E ¹ is a single bond,
In formula XIV:
R and Q are as described above for each of I, II, III, IV, V, VI, VII, VIII to XI, and E ¹ is a single bond)
In each of

(Formula II)
The second monomer unit can be an aromatic group having the structure shown in FIG. 2, Formula II. The R group is preferably hydrogen,
Alkyl,
Aryl,
Heteroalkyl,
Heteroaryl,
F,
-CN,
-NO _2,
Beta-dicarbonyl as described above, having the formula XII shown in FIG.
-C _Ψ H _θ F _λ ,
_-OC Ψ H θ F _λ, and ^{_{-P (R 1) 2, -SOR}} 1, from ^{_{-OR 1, -CO 2 R 1,}} -SR 1, -N (R 1) 2, and _-SO 2 ^{R 1} Wherein R ¹ is a linear or branched alkyl or linear or branched heteroalkyl of ¹ to 20 carbons, or adjacent R groups taken together to form a cycloalkyl ring, aryl 5- or 6-membered rings selected from rings and heteroaryl rings can be formed.

Alternatively, the R group in formula II is
An alkyl group having 1 to 12 carbon atoms,
A partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, in particular CF ₃ ,
An aryl group having 6 to 20 carbon atoms,
A heteroaryl group having from 4 to 20 carbon atoms and substituted with O, S, or N;
Selected from alkoxy groups having 1 to 12 carbon atoms and esters having 3 to 15 carbon atoms.

Examples of suitable second monomer units of formula II are the formulas II (a) to II (z) in FIGS.
In formulas II (v) to II (y):
R is as described above for each of formulas I, II, III, IV, V, VI, VII, VIII to XI)
As shown.

(Formula III)
Alternatively, the second monomer unit can be a divalent 6-membered heteroaromatic group having the structure shown in FIG. 6, Formula III. Preferred R groups are _hydrogen, C 1 _{-C 12} alkyl group _{(alternatively,} C 1 -C ₅ alkyl or _C 6 _{-C 12} alkyl _group), C 6 _{-C 20} aryl groups, and _C 2 _{-C 20} hetero An aryl group. Examples of suitable E linking groups include pyridinediyl (—C ₅ H ₄ N—) and bipyridinediyl (—C ₅ H ₄ N—C ₅ H ₄ N—).

  Examples of suitable second monomer units having formula III are shown in FIG. 6 as formulas II (a) to III (g).

(Formula IV)
Alternatively, the second monomer unit can be a 5-membered heteroaromatic group having the structure shown in FIG. 7, Formula IV. Preferred R groups are _hydrogen, C 1 _{-C 12} alkyl group _{(alternatively,} C 1 -C ₆ alkyl or _C 6 _{-C 12} alkyl _{group), C} 6 ~C ₂₀ aryl group _{(alternatively,} C 6 _{-C 10} aryl group), and _C 2 _{-C 20} heteroaryl group _{(alternatively,} C 6 _{-C 10} heteroaryl group), more preferably a _C 6 _{-C 12} aryl group. Examples of suitable E linking groups include pyrrole diyl (—C ₄ H ₃ N—) and thiophene diyl (—C ₄ H ₃ S—).

Examples of suitable second monomer units of formula IV are formulas IV (a) to IV (h) (where
In formula IV (a):
R is as described above for each of Formulas I, II, III, IV, V, VI, VII, VIII to XI, and in Formula IV (h):
R ¹ is a substituent on the heteroatom that may be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl)
Shown as

(Formula V)
Alternatively, the second monomer unit can be aromatic having the structure shown in FIG. R group is preferably _hydrogen, C 1 _{-C 12} alkyl group _{(alternatively,} C 1 -C ₆ alkyl or _C 6 _{-C 12} alkyl _{group), C} 6 ~C ₂₀ aryl group _{(alternatively,} C 6 -C ₁₀ aryl group), and _C 2 _{-C 20} heteroaryl group (or _{alternatively,} a C 6 _{-C 10} heteroaryl group). Preferably two W represent one single bond.

Examples of suitable second monomer units of this type have the structure of formula V (a) to formula V (e)
here,
In formulas V (a) and V (b):
R is as described above for each of Formulas I, II, III, IV, V, VI, VII, VIII to XI, and in Formula V (e):
R ¹ is a substituent on the heteroatom that may be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl.

(Formulas VI to XI)
Alternatively, the second monomer unit can be a divalent fused ring aromatic group having the structure shown in FIG. 9, Formulas VI to VIII, and FIG. 10, Formulas IX to XI. R group is preferably _hydrogen, C 1 _{-C 20} alkyl group _{(alternatively,} C 1 -C ₆ alkyl or _C 6 _{-C 12} alkyl _group), C 6 _{-C 20} aryl groups, and _C 2 _{-C 20} hetero An aryl group.

  In formula VI, E is preferably in the 1,4-, 1,5-, 1,8-, 2,3-, or 2,6-position. Examples of suitable second monomer units having the formula VI are shown in FIG. 9, formulas VI (a) to VI (d).

  In formula VII, E is preferably in the 1,4-, 1,5-, 1,8-, 2,3-, 2,6-, or 9,10-position. An example of a suitable second monomer unit having formula VII is shown in FIG. 10, formula VII (a).

  In the copolymer of the present invention, the R group is essentially a side chain from the polymer backbone. Thus, the final choice of R groups should take into account the role these side chains may play in the properties of the final polymer. These properties include high dielectric constants to solvate ions to enhance or reduce interchain interactions, induce solubility in organic solvents, and induce compatibility with host polymers in the blend. Electronic properties, solubility characteristics, processing characteristics, film-forming characteristics, etc. are included to induce rate, to increase ion mobility. Furthermore, if the R group is substituted, the steric effects of such substituents should be taken into account when selecting substituents.

  In the fluorene polymer of the present invention, two or more of the second monomer units may be present together with the first monomer unit. The relative molar ratio of the first monomer unit to the at least one second monomer unit is 99.9: 0.1 to 1:99 or 99.5: 0.5 to 10:90, or alternatively 99: 1 to It can be 20:80, and also alternatively 99: 1 to 50:50. Molecular weights can vary from thousands to hundreds of thousands. Incorporation of monomers in the formation of the polymer is random or can be controlled, resulting in copolymers including but not limited to random copolymers, alternating copolymers and block copolymers.

Fluorene polymers of the present invention, (wherein, [psi to 20, preferably a is an integer of 1 to 12) wherein _{-C Ψ} F 2Ψ _{+ 1} contains at least one R substituent having. A perfluoroalkyl group is a substituent on an aromatic ring. The proportion of monomer units having perfluoroalkyl substitution is generally in the range of 5 to 100 mole percent, preferably 10 to 50 mole percent.

(Method)
The perfluoroalkylated fluorene polymers of the present invention can be prepared by first forming a perfluoroalkylated monomer and then polymerizing to form a polymer. However, such an approach requires a separate synthesis for each monomer, which can be difficult. In another embodiment of the present invention, a more versatile method for the preparation of perfluoroalkylated fluorene polymers, comprising first preparing a base fluorene polymer, and then converting the base polymer to perfluoroalkyl groups. Treating with a material that can be introduced into the aromatic ring of the polymer.

  The polymerization to form the base fluorene polymer can generally be carried out by three known synthetic routes. In the first synthesis method as described in (Non-Patent Document 1), the monomer unit dihalo, preferably the dibromo derivative, is a stoichiometric amount of bis (1,5-cyclooctadiene) nickel (0). And a zero-valent nickel compound such as In the second method as described in (Non-Patent Document 2), the presence of a stoichiometric amount of a substance in which the dihalo derivative of the monomer unit can reduce divalent nickel ions to zero-valent nickel. Below, it is reacted with a catalytic amount of Ni (II) compound. Suitable materials include zinc, magnesium, calcium and lithium. In a third synthesis method such as described in US Pat. Nos. 3,048, and 4,049, a monomonomeric dihalo derivative is a zero valent, such as tetrakis (triphenylphosphine) Pd. In the presence of a palladium catalyst, it is reacted with a derivative of another monomer unit having two reactive groups selected from boric acid, borate esters, and borane. This third reaction can occur in a two-phase medium that requires a phase transfer catalyst.

  In some embodiments of the invention, the polymer can be reacted with an end-capping compound to convert reactive end groups to non-reactive end groups. The end-capping compound is generally added to the preformed polymer to terminate the polymerization reaction. End-capping compounds are generally aromatic compounds with only one reactive group, such as an aromatic ring with only one halide group or boric acid or ester group. Examples of suitable end-capping compounds include 9-bromoanthracene, 4-bromo-1,2-dimethoxybenzene, 1-bromopyrene, iodobenzene, bromobenzene, 2-bromo-9-fluorenone, benzeneboric acid, and 4 -Methylbenzeneboric acid is included. End-capping groups may also be designed to add functionality such as charge transport properties and color shift. It may also affect interchain aggregation.

  After the base fluorene polymer is formed, it is reacted with a perfluoroalkylating agent selected from (i) perfluoroalkyl iodide and (ii) perfluoroalkylsulfonyl chloride in the presence of a ruthenium (II) catalyst. It is done.

  Suitable perfluoroalkyl iodides include those having 1-20, preferably 1-12 carbon atoms, which may be linear, branched or cyclic. A number of perfluoroalkyl iodides are commercially available. Others can be made by well-known synthetic techniques.

  Suitable perfluoroalkylsulfonyl chlorides include those having 1-20, preferably 1-12 carbon atoms, which may be linear, branched or cyclic. A number of perfluoroalkylsulfonyl chlorides are commercially available. Others can be made by well-known synthetic techniques.

  Suitable ruthenium (II) catalysts are neutral organometallic complexes with phosphines, especially ligands such as triphenylphosphine, carbon monoxide, cyclooctadiene, chloride, and hydride. A preferred catalyst is dichlorotris (triphenylphosphine) ruthenium (II). A number of ruthenium (II) catalysts are commercially available. Others can be produced by a well-known synthesis technique as disclosed in, for example, (Non-Patent Document 3).

  The perfluoroalkylation reaction is generally carried out in a solvent in which the base fluorene polymer is at least partially soluble in it that does not react with the perfluoroalkylating agent. Examples of suitable solvents include electron deficient aromatic compounds such as chlorobenzenes. If higher reaction temperatures are needed, higher boiling solvents are used. The reaction is generally carried out in an inert atmosphere such as under nitrogen. The temperature is generally about 100 ° C to 250 ° C. The reaction time can vary from about 1 hour to 3 days. The reaction product can be isolated using known techniques such as extraction or precipitation with a second solvent, and drying.

  The resulting product will have perfluoroalkyl groups substituted on at least some of the aromatic rings in the polymer. The number of perfluoroalkyl substituents per polymer and their position, ie which aromatic group is substituted, depends on the chemical reactivity of the monomer units that make up the polymer. The three-dimensional effect may be a factor.

  Perfluoroalkylation of fluorene polymers and copolymers affects the electronic properties of the polymer. Perfluoroalkylated fluorene polymers are more electron deficient and have lower LUMO levels. This increases the conductivity of the polymer and facilitates electron injection / transport. Perfluoroalkylation will also affect other polymer properties such as polymer film solubility, processability, and morphology.

(Electronic device)
The invention also relates to an electronic device comprising at least one photoactive layer placed between two electrical contact layers, the at least one electroactive layer of which comprises a copolymer of the invention. Related. As shown in FIG. 13, a typical device 100 has an anode layer 110 and a cathode layer 150, and electroactive layers 120, 130 and optionally 140 between the anode 110 and the cathode. Adjacent to the anode is a hole injection / transport layer 120. Adjacent to the cathode is an optional layer 140 comprising an electron transport material. There is a photoactive layer 130 between the hole injection / transport layer 120 and the cathode (or any electron transport layer). The copolymers of the present invention may be useful in the hole injection / transport layer 120 and / or in the photoactive layer 130 and / or any electron injection / transport layer 140.

  The device generally also includes a support (not shown) that may be adjacent to the anode or cathode. Most often, the support is adjacent to the anode. The support can be organic or inorganic, which can be flexible or rigid. In general, glass or flexible organic films are used as the support. The anode 110 is an electrode that is particularly efficient for injecting or collecting positive charge carriers. The anode is preferably made from a material comprising a metal, mixed metal, alloy, metal oxide or mixed metal oxide. Suitable metals include Group 11 metals, Group 4, 5, and 6 metals, and Group 8-10 transition metals. Where the anode should be light transmissive, mixed metal oxides of Group 12, 13, and 14 metals, such as indium-tin-oxide, are generally used. The anode 110 may also include an organic material such as polyaniline as described in (Non-Patent Document 4).

  The anode layer 110 is typically deposited by physical vapor deposition or spin-coating. The term “physical vapor deposition” refers to various deposition methods performed in vacuum. Thus, for example, physical vapor deposition includes all forms of sputtering, including ion beam sputtering, as well as all forms of deposition, such as electron beam evaporation and resistance evaporation. A specific form of physical vapor deposition that is useful is radio frequency magnetron sputtering.

The copolymer of the present invention may serve as a hole injection / transport material in layer 120. Other materials that may facilitate hole injection / transport include N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4 ′. Diamine (TPD) and bis [4- (N, N-diethylamino) -2-methylphenyl] (4-methylphenyl) methane (MPMP), and polyvinylcarbazole (PVK), (phenylmethyl) polysilane, poly (3 , 4-ethylenedioxythiophene) (PEDOT), and hole injection / transport polymers such as polyaniline (PANI), electrons and holes such as 4,4'-N, N'-dicarbazole biphenyl (BCP) injecting / transporting material or tris (8-hydroxyquinolato) such as aluminum (Alq _3), chelated oxinoid (oxinoid) compound, Luminescent material which good electron and hole injection / transport properties include.

  The hole injection / transport layer 120 can be deposited using any conventional method, including printing such as spin-coating, casting, and gravure printing. The layer can also be deposited by ink jet printing, thermal patterning, or physical vapor deposition.

  In general, the inorganic anode and hole injection / transport layer 120 will be patterned. It will be appreciated that the pattern may vary as desired. The layer can be deposited in a pattern, for example by placing a patterned mask or photoresist on the first flexible composite barrier structure prior to depositing the first electrical contact layer material. Alternatively, the layer can be deposited as an overall layer and then patterned using, for example, photoresist and wet chemical etching. The hole injection / transport layer can also be deposited in a pattern by ink jet printing, lithography or thermal transfer patterning. Other methods for patterning that are well known in the art can also be used.

  Depending on the application of the device 100, the photoactive layer 130 is responsive to radiant energy with or without a light emitting layer (such as in a light emitting diode or light emitting electrochemical cell) activated by an applied voltage. It can be a layer of material (such as in a photodetector) that generates a signal. Examples of photodetectors include photoconductive cells, photoresistors, optical switches, phototransistors, and phototubes, and photovoltaic cells, as these terms are described in (Non-Patent Document 5).

  If device 100 is a light emitting device, photoactive layer 130 will emit light when a sufficient bias voltage is applied to the electrical contact layer. The copolymer of the present invention may be used for the light emitting active layer 130. Other known light-emitting materials include, for example, US Patent Publication (US Pat. No. 5,677,097) by Tang, US Patent Publication by Van Slyke et al., The relevant portions of which are incorporated herein by reference. Small molecule materials such as those described in US Pat. Alternatively, such materials are disclosed in U.S. Patents (Patent Document 7) by Friends et al., U.S. Patent Publications (Heiger) et al. (Patent Document 8), the relevant portions of which are incorporated herein by reference. Can be polymeric materials such as those described in Nakano et al., US Pat. The luminescent material may be dispersed in a matrix of another material with or without additives, but preferably forms only a layer. The active organic layer generally has a thickness in the range of 50 to 500 nm.

  When the electronic device 100 is a photodetector, the photoactive layer 130 generates a signal in response to radiant energy, either with or without a biased voltage. Materials that can generate a signal in response to radiant energy with a biased voltage (such as in photoconductive cells, photoresistors, optical switches, phototransistors, phototubes) include, for example, multiconjugated polymers and electro A luminescent material is included. Materials that can generate a signal in response to radiant energy without a biasing voltage (such as in the case of a photoconductive cell or photovoltaic cell) include materials that chemically react to light and thereby generate a signal. included. Such photoelectrically chemically reactive materials include, for example, multiconjugated polymers and electro- and photo-luminescent materials. Specific examples include, but are not limited to, MEH-PPV (Non-Patent Document 6) and MEH-PPV composite material with CN-PPV (Non-Patent Document 7).

  The active layer 130 containing the active organic material can be applied from solution by any conventional method including spin-coating, casting, and printing. The active organic material can be deposited directly by vapor deposition, depending on the nature of the material. It is also possible to apply the active polymer precursor and then convert it to a polymer, typically by heating.

  The cathode 150 is an electrode that is particularly efficient for injecting or collecting electrons or negative charge carriers. The cassault can be any metal or non-metal that has a lower work function than the first electrical contact layer (in this case, the anode). The material for the second electrical contact layer can be selected from Group 1 alkali metals (eg, Li, Cs), Group 2 (alkaline earth) metals, Group 12 metals, rare earths, lanthanides, and actinides. aluminum. Materials such as indium, calcium, barium, and magnesium and combinations can be used.

  Cathode layer 150 is typically deposited by physical vapor deposition. In general, the cathode layer will be patterned as discussed above with respect to the anode layer 110 and the conductive polymer layer 120. Similar processing techniques can be used to pattern the cathode layer.

Optional layer 140 can serve both functions to promote electron transport and also serve as a buffer or confinement layer to prevent deactivation reactions at the layer interface. Preferably, this layer promotes electron mobility and reduces deactivation reactions. Examples of electron transport materials for the optional layer 140 include metal chelated oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq ₃ ), 2,9-dimethyl-4,7-diphenyl-1, Phenanthroline-based compounds such as 10-phenanthroline (DDPA) or 4,7-diphenyl-1,10-phenanthroline (DPA), and 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1, Azole compounds such as 3,4-oxadiazole (PBD) and 3- (4-biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (TAZ) included.

  It is known to have other layers in organic electronic devices. For example, between the conductive polymer layer 120 and the active layer 130 to promote positive charge transport and / or band-gap matching of the layer, or to serve as a protective layer There may be a layer (not shown). Similarly, additional layers (shown between active layer 130 and cathode layer 150 are shown to facilitate negative charge transport and / or band-gap matching between layers or to serve as a protective layer. May not exist). Layers known in the art can be used. Furthermore, any of the layers described above can be made from two or more layers. Alternatively, some or all of the inorganic anode layer 110, the conductive polymer layer 120, the active layer 130, and the cathode layer 150 may be surface treated to increase charge carrier transport efficiency. The selection of materials for each of the component layers is preferably determined by comparing the goal of providing a device with high device efficiency.

  Device 100 can be prepared by sequentially depositing the individual layers on a suitable substrate. Substrates such as glass and polymer films can be used. In most cases, the anode is attached to the substrate from which the layers are grown. However, it is possible to first attach the cathode to the substrate and add the layers in the reverse order. In general, the different layers have thicknesses in the following ranges: inorganic anode 110, 500 to 5000 mm, preferably 1000 to 2000 mm; conductive polymer layer 120, 50 to 2500 mm, preferably 200 to 2000 mm; It will have 1000 電子, preferably 100-800５０; optional electron transport layer 140, 50-1000Å, preferably 200-800Å; cathode 150, 200-10000Å, preferably 300-5000Å.

  The following examples illustrate certain features and advantages of the present invention. They are intended to illustrate but not limit the invention. All percentages are by weight unless otherwise specified.

(Example 1)
This example illustrates the preparation of a base fluorene polymer, 2,7-poly (9,9-bis (2-ethylhexyl) fluorene).

Bis (1,5-cyclooctadiene) nickel (0) (2.231 g, 8.11 mmol), 2,2′-bipyridyl (1.267 g, 8.11) with a stir bar under inert conditions. Mmol), and DMF (5 ml) to a 50 ml Schlenck tube containing 1,5-cyclooctadiene (0.877 g, 8.11 mmol). The resulting deep blue / purple solution was stirred at 60 ° C. for 30 minutes and then 2,7-dibromo-9,9-bis (2-ethylhexyl) fluorene (2.00 g, 3.65 mmol) in toluene (20 ml). Was added by syringe. The reaction mixture was then stirred at 75 ° C. for 5 days. The mixture was cooled to room temperature and precipitated into a solution of methanol (100 ml), acetone (100 ml) and concentrated hydrochloric acid (5 ml). After stirring for 2 hours, the mixture was filtered. The solid residue was then dissolved in chloroform and reprecipitated by adding it to a solution of methanol (100 ml), acetone (100 ml) and concentrated hydrochloric acid (5 ml). After stirring for 1 hour, the mixture was filtered. Finally, the residue was washed successively with methanol, water and methanol and dried in vacuo. The copolymer was characterized by nuclear magnetic resonance (NMR) and the number average molecular weight (M _n ) was measured by gel permeation chromatography (GPC).

Example 1A
The procedure of Example 1 was repeated except that the reaction mixture was stirred at 75 ° C. for 24 hours instead of 5 days. Further, after the mixture was filtered, the residue was washed successively with methanol, water and methanol, and the resulting solid was redissolved in chloroform and precipitated in pure methanol before vacuum drying. Essentially the same molecular weight as given in Table 1 below was obtained.

(Examples 2 to 4)
Examples 2-4 illustrate the preparation of perfluoroalkylated fluorene copolymers of the present invention.

(Example 2)
In this example, a perfluorodecyl substituent was added to the base fluorene polymer from Example 1.

In a 100 ml round bottom flask equipped with a water cooler under nitrogen atmosphere, 2,7-poly (9,9-bis (2-ethylhexyl) fluorene) from Example 1 (0.50 g, 1.29 mmol), 1-Iodoperfluorodecane (1.83 g, 2.84 mmol) and 1,2,4-trichlorobenzene (50 ml) were charged. The vessel was then heated to 190 ° C. for 24 hours. After cooling to room temperature, the reaction solution was extracted with chloroform. The chloroform layer was washed successively with a dilute sodium hydrogen sulfite aqueous solution, a dilute sodium hydrogen carbonate aqueous solution, a dilute sodium hydroxide aqueous solution, and water. The organic layer was dried over magnesium sulfate and then evaporated to dryness, and the resulting polymer was analyzed by F ¹⁹ nmr, which showed approximately 10-15 mole percent perfluorodecyl group addition.

(Example 3)
In this example, a perfluoromethyl substituent was added to the base fluorene polymer from Example 1.

Under a nitrogen atmosphere, in a glass pressure vessel, 2,7-poly (9,9-bis (2-ethylhexyl) fluorene) from Example 1 (0.50 g, 1.29 mmol), trifluoromethanesulfonyl chloride (0. 48 g, 2.84 mmol), dichlorotris (triphenylphosphine) ruthenium (II) (12 mg, 0.0125 mmol) and 1,2,4-trichlorobenzene (20 ml) were charged. The vessel was cooled to −30 ° C. in a dry ice / acetone bath, evacuated, and then flushed with nitrogen. This cycle was repeated twice more. The vessel was then warmed to room temperature and placed in an autoclave where it was heated to 130 ° C. for 24 hours. The vessel was then cooled to room temperature and purged with nitrogen. The trichlorobenzene solution was added into acetone and precipitated. The solid residue was collected, washed with acetone and dried in vacuo. The resulting polymer was analyzed by F ¹⁹ NMR which showed approximately 10-15 mole percent perfluoromethyl group addition.

(Example 4)
In this example, a perfluorobutyl substituent was added to the base fluorene polymer from Example 1.

In a 100 ml round bottom flask equipped with a water cooler under nitrogen atmosphere, 2,7-poly (9,9-bis (2-ethylhexyl) fluorene) from Example 1 (0.50 g, 1.29 mmol), Charged with perfluorobutylsulfonyl chloride (0.905 g, 2.84 mmol), dichlorotris (triphenylphosphine) ruthenium (II) (12 mg, 0.0125 mmol) and 1,2,4-trichlorobenzene (20 ml). did. The vessel was then heated to 120 ° C. for 24 hours. After cooling the container to room temperature, the reaction solution was added into acetone to precipitate. The solid residue was collected, washed with acetone and dried in vacuo. The resulting polymer was analyzed by F ¹⁹ nmr, which showed approximately 10-15 mole percent perfluorobutyl group addition.

  Although the present invention has been described with respect to what is presently considered to be the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, the invention is intended to cover various modifications and equivalents falling within the spirit and scope of the appended claims. The following claims should be accorded the broadest interpretation to encompass all such modifications and equivalent formulations and functions.

Formula I and Formula I (a) for the first monomer unit useful in the present invention are shown. Figure 2 illustrates Formula II for a second monomer unit useful in the present invention. Formula II (a) to II (j) for the second monomer unit useful in the present invention is shown. Formula II (k) to II (s) for the second monomer unit useful in the present invention is shown. Formula II (t) to II (z) for the second monomer unit useful in the present invention is shown. Formula III and Formulas III (a) to III (g) for the second monomer unit useful in the present invention are shown. Formula IV and Formulas IV (a) to IV (h) for the second monomer unit useful in the present invention are shown. Formula V and Formulas V (a) to V (e) for the second monomer unit useful in the present invention are shown. Formula VI and Formulas VI (a) to VI (d) for the second monomer unit useful in the present invention are shown. Figures VII and VII (a) for the second monomer unit useful in the present invention are shown. Formulas VIII to XI for the second monomer unit useful in the present invention are shown. Formula XII for a substituent for the second monomer unit useful in the present invention is shown. 1 is a schematic illustration of an electronic device that can incorporate the perfluoroalkylated fluorene polymer of the present invention.

Claims (12)

A polymer comprising one or more first monomer units having the formula I shown in FIG.
Where
R is a substituent on a carbon atom in the aromatic ring, which may be the same or different at each occurrence, and is hydrogen, alkyl, aryl, heteroalkyl, heteroaryl, F, —CN, —OR ¹ , _{^{-CO 2 R 1, -C Ψ H}} θ F λ, -OC Ψ H θ F λ, -SR 1, -N (R 1) 2, -P (R 1) 2, -SOR 1, -SO 2 R ¹ , —NO ₂ , and beta-dicarbonyl having the formula XII shown in FIG. 12, or adjacent R groups together are 5-membered cycloalkyl, 6-membered cycloalkyl, 5-membered aryl A ring selected from 6-membered aryl, 5-membered heteroaryl and 6-membered heteroaryl,
Wherein R ¹ is a substituent on the heteroatom that may be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl, and ψ is between 1 and 20 And θ and λ are the following equations A1:
θ + λ = 2Ψ + 1 (Equation A1)
Is an integer that satisfies
R ² is a substituent on a carbon atom not in the aromatic ring that may be the same or different at each occurrence, and is hydrogen, alkyl, aryl, heteroalkyl, heteroaryl, and —C _ψ H _θ F _λ Selected from
However, polymers characterized in that it comprises at least one R substituent having the formula _-C Ψ F 2Ψ _{+ 1.} A polymer further comprising at least one second monomer unit, wherein the second monomer unit is (i) an aromatic group having the formula I shown in FIG. 1, and (ii) the formula II shown in FIG. (Iii) a 6-membered heteroaromatic group having the formula III shown in FIG. 6, (iv) a 5-membered heteroaromatic group having the formula IV shown in FIG. 7, (v) FIG. (Vi) a divalent fused ring aromatic group having the formula VI to formula VIII shown in FIG. 9 and the formula IX to formula XI shown in FIG. 10, and (vii) ) Selected from those combinations,
here,
In each of formulas II, III, IV, V, VI, VII, VIII and IX:
R, R ¹ , R ² , Ψ, θ and λ are as defined above;
E can be the same or different at each occurrence and is a single bond or a linking group selected from arylene and heteroarylene;
In formula IV:
A is independently C or N at each occurrence, and γ is an integer selected from 0 or 1 or 2, where when both A are N, γ is 0, or A Γ is 1 when one of N is N and one of A is C, or γ is 2 when both A are C;
Q is O, S, SO ₂ or NR ¹ (where
R ¹ is a substituent on the heteroatom that may be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl)
In formula V:
Q ¹ is a carbonyl group, O, S, SO ₂ , or NR ¹ (wherein
R ¹ is a substituent on the heteroatom that may be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl)
W is H, alkyl or heteroalkyl, or both W together can represent a single bond;
In Formula VI:
The two E's are in the 1,4-, 1,5-, 1,8-, 2,3-, or 2,6-position;
In Formula VII:
The two E's are in the 1,4-, 1,5-, 1,8-, 2,3-, 2,6-, or 9,10-position;
In Formula VIII:
The first E is in the 1, 2, or 3rd position, the second E is in the 6, 7 or 8th position,
In formula IX:
The first E is in the 2, 3, or 4th position, the second E is in the 7, 8, or 9th position, and
In Formula XII:
R ³ is selected from hydrogen, alkyl, aryl, heteroalkyl and heteroaryl;
The polymer according to claim 1, wherein δ is 0 or an integer of 1 to 12.   At least one of the R groups in one or more of the at least one first monomer unit is a linear and branched n-butyl group, a linear and branched isobutyl group, a linear and branched pentyl group; 3. Independently selected from hexyl and octyl groups with or without olefinic unsaturation, phenyl groups, thiophene groups, carbazole groups, alkoxy groups, phenoxy groups and cyano groups Polymer. At least one R group in one or more of the at least one first monomer unit is independently selected from H, C ₆ -C ₁₂ alkoxy, phenoxy, C ₆ -C ₁₂ alkyl, phenyl and cyano. The polymer according to claim 2. One or more of the at least one second monomer unit is of formula II (a) to II (z), III (a) to III (g), IV (a) to IV (h), V (a) To V (e), VI (a) to VI (d), and VII (a),
here,
In formulas II (v) to II (y), IV (a), V (a), and V (b):
R is as described above for each of Formulas I, II, III, IV, V, VI, VII, VIII to XI;
In formula IV (h):
R ¹ is a substituent on the heteroatom that may be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl, and in Formula V (e):
Polymer according to claim 2, characterized in that R ¹ is a substituent on the heteroatom which can be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl . At least one second monomer unit has the formula II;
Where R is hydrogen,
Alkyl,
Aryl,
Heteroalkyl,
Heteroaryl,
F,
-CN,
-NO _2,
Beta-dicarbonyl having the formula XII shown in FIG. 12,
-C _Ψ H _θ F _λ ,
_-OC Ψ H θ F _λ, and -P ^(R ₁₎ ^2, from _{^{-SOR 1, -OR 1, -CO 2}} R 1, -SR 1, -N (R 1) 2, and _-SO 2 ^{R 1} Selected
2. The polymer according to claim 1, wherein R ¹ is a linear or branched alkyl or linear or branched heteroalkyl of ¹ to 20 carbons. One or more of the at least one second monomer unit has the formula II;
Where R is
An alkyl group having 1 to 12 carbon atoms,
A partially or fully fluorinated alkyl group having 1 to 12 carbon atoms, in particular CF ₃ ,
An aryl group having 6 to 20 carbon atoms,
A heteroaryl group having from 4 to 20 carbon atoms and substituted with O, S, or N;
2. The polymer according to claim 1, wherein the polymer is selected from alkoxy groups having 1 to 12 carbon atoms and esters having 3 to 15 carbon atoms.   The polymer according to claim 1, further comprising an end capping group including an aromatic group.   Electronic device (100), characterized in that it comprises at least one electroactive layer (120, 130, 140) comprising a polymer according to any one of claims 1-7.   The one or more of the at least one electroactive layer is a photoactive layer (130), or a hole injection / transport layer (120), or an electron injection / transport layer (140). The device described.   The device of claim 9, wherein the device is selected from a light emitting device, a photodetector, and a photovoltaic device. A method for preparing a polymer according to any one of claims 1-7, comprising:
Forming a polymer having at least one first monomer unit having the formula I shown in FIG.
Where
R is a substituent on a carbon atom in the aromatic ring, which may be the same or different at each occurrence, and is hydrogen, alkyl, aryl, heteroalkyl, heteroaryl, F, —CN, —OR ¹ , _{^{-CO 2 R 1, -C Ψ H}} θ F λ, -OC Ψ H θ F λ, -SR 1, -N (R 1) 2, -P (R 1) 2, -SOR 1, -SO 2 R ¹ , —NO ₂ , and beta-dicarbonyl having the formula XII shown in FIG. 12, or adjacent R groups together are 5-membered cycloalkyl, 6-membered cycloalkyl, 5-membered aryl A ring selected from 6-membered aryl, 5-membered heteroaryl and 6-membered heteroaryl,
here,
R ¹ is a substituent on the heteroatom that may be the same or different at each occurrence and is selected from alkyl, aryl, heteroalkyl and heteroaryl, and ψ is an integer between 1 and 20 And θ and λ are the following equations A1:
θ + λ = 2Ψ + 1 (Equation A1)
Is an integer that satisfies
R ² is a substituent on a carbon atom not in the aromatic ring that may be the same or different at each occurrence, and is hydrogen, alkyl, aryl, heteroalkyl, heteroaryl, and —C _ψ H _θ F _λ Selected from
However, the polymer includes the steps of including at least one R substituent having the formula _-C Ψ F 2Ψ _{+ 1,}
Treating the polymer with a perfluoroalkylating agent selected from (i) perfluoroalkyl iodide and (ii) perfluoroalkylsulfonyl chloride in the presence of a ruthenium (II) catalyst. how to.

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